EP2493903A1 - Verfahren zur herstellung von konjugierten dienphosphonatverbindungen - Google Patents
Verfahren zur herstellung von konjugierten dienphosphonatverbindungenInfo
- Publication number
- EP2493903A1 EP2493903A1 EP09850739A EP09850739A EP2493903A1 EP 2493903 A1 EP2493903 A1 EP 2493903A1 EP 09850739 A EP09850739 A EP 09850739A EP 09850739 A EP09850739 A EP 09850739A EP 2493903 A1 EP2493903 A1 EP 2493903A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- carbon atoms
- cycloalkyl
- conjugated diene
- represent
- heterocycloalkyl
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
- 238000000034 method Methods 0.000 title claims abstract description 44
- -1 diene phosphonate compounds Chemical class 0.000 title claims abstract description 24
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims abstract description 37
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims abstract description 26
- 229920000642 polymer Polymers 0.000 claims abstract description 18
- 150000002576 ketones Chemical class 0.000 claims abstract description 17
- 239000000203 mixture Substances 0.000 claims abstract description 16
- ISIJQEHRDSCQIU-UHFFFAOYSA-N tert-butyl 2,7-diazaspiro[4.5]decane-7-carboxylate Chemical compound C1N(C(=O)OC(C)(C)C)CCCC11CNCC1 ISIJQEHRDSCQIU-UHFFFAOYSA-N 0.000 claims abstract description 16
- 150000001299 aldehydes Chemical class 0.000 claims abstract description 13
- 229920001577 copolymer Polymers 0.000 claims abstract description 12
- 238000006243 chemical reaction Methods 0.000 claims description 25
- 125000004432 carbon atom Chemical group C* 0.000 claims description 24
- 150000001875 compounds Chemical class 0.000 claims description 20
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 16
- 125000000592 heterocycloalkyl group Chemical group 0.000 claims description 14
- 125000003118 aryl group Chemical group 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- 125000000217 alkyl group Chemical group 0.000 claims description 11
- 125000003342 alkenyl group Chemical group 0.000 claims description 10
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 10
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 7
- 239000003063 flame retardant Substances 0.000 claims description 7
- 150000002431 hydrogen Chemical class 0.000 claims description 5
- 229920003023 plastic Polymers 0.000 claims description 5
- 239000004033 plastic Substances 0.000 claims description 5
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 229910052751 metal Inorganic materials 0.000 claims description 3
- 239000002184 metal Substances 0.000 claims description 3
- 238000005065 mining Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 238000004381 surface treatment Methods 0.000 claims description 3
- 150000002739 metals Chemical class 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- JJCFRYNCJDLXIK-UHFFFAOYSA-N cyproheptadine Chemical compound C1CN(C)CCC1=C1C2=CC=CC=C2C=CC2=CC=CC=C21 JJCFRYNCJDLXIK-UHFFFAOYSA-N 0.000 claims 1
- 239000000178 monomer Substances 0.000 abstract description 23
- 150000001993 dienes Chemical class 0.000 abstract description 13
- UEZVMMHDMIWARA-UHFFFAOYSA-M phosphonate Chemical group [O-]P(=O)=O UEZVMMHDMIWARA-UHFFFAOYSA-M 0.000 abstract description 9
- 230000009257 reactivity Effects 0.000 abstract description 8
- ABLZXFCXXLZCGV-UHFFFAOYSA-N phosphonic acid group Chemical group P(O)(O)=O ABLZXFCXXLZCGV-UHFFFAOYSA-N 0.000 description 19
- OZXIZRZFGJZWBF-UHFFFAOYSA-N 1,3,5-trimethyl-2-(2,4,6-trimethylphenoxy)benzene Chemical compound CC1=CC(C)=CC(C)=C1OC1=C(C)C=C(C)C=C1C OZXIZRZFGJZWBF-UHFFFAOYSA-N 0.000 description 10
- SHOJXDKTYKFBRD-UHFFFAOYSA-N mesityl oxide Natural products CC(C)=CC(C)=O SHOJXDKTYKFBRD-UHFFFAOYSA-N 0.000 description 10
- 239000000047 product Substances 0.000 description 10
- 238000005481 NMR spectroscopy Methods 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 8
- 239000000543 intermediate Substances 0.000 description 7
- 230000008569 process Effects 0.000 description 7
- 150000008064 anhydrides Chemical class 0.000 description 6
- 150000001728 carbonyl compounds Chemical class 0.000 description 6
- 230000007246 mechanism Effects 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 4
- ULDHMXUKGWMISQ-UHFFFAOYSA-N carvone Chemical compound CC(=C)C1CC=C(C)C(=O)C1 ULDHMXUKGWMISQ-UHFFFAOYSA-N 0.000 description 4
- 230000018044 dehydration Effects 0.000 description 4
- 238000006297 dehydration reaction Methods 0.000 description 4
- 238000006116 polymerization reaction Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000011541 reaction mixture Substances 0.000 description 4
- 238000003756 stirring Methods 0.000 description 4
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 description 3
- RNFJDJUURJAICM-UHFFFAOYSA-N 2,2,4,4,6,6-hexaphenoxy-1,3,5-triaza-2$l^{5},4$l^{5},6$l^{5}-triphosphacyclohexa-1,3,5-triene Chemical compound N=1P(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP(OC=2C=CC=CC=2)(OC=2C=CC=CC=2)=NP=1(OC=1C=CC=CC=1)OC1=CC=CC=C1 RNFJDJUURJAICM-UHFFFAOYSA-N 0.000 description 3
- 238000004679 31P NMR spectroscopy Methods 0.000 description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 3
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 3
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 description 3
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000003814 drug Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 230000000269 nucleophilic effect Effects 0.000 description 3
- 229950000688 phenothiazine Drugs 0.000 description 3
- 230000008707 rearrangement Effects 0.000 description 3
- 239000002904 solvent Substances 0.000 description 3
- DCSCXTJOXBUFGB-JGVFFNPUSA-N (R)-(+)-Verbenone Natural products CC1=CC(=O)[C@@H]2C(C)(C)[C@H]1C2 DCSCXTJOXBUFGB-JGVFFNPUSA-N 0.000 description 2
- DCSCXTJOXBUFGB-SFYZADRCSA-N (R)-(+)-verbenone Chemical compound CC1=CC(=O)[C@H]2C(C)(C)[C@@H]1C2 DCSCXTJOXBUFGB-SFYZADRCSA-N 0.000 description 2
- LLVWLCAZSOLOTF-UHFFFAOYSA-N 1-methyl-4-[1,4,4-tris(4-methylphenyl)buta-1,3-dienyl]benzene Chemical compound C1=CC(C)=CC=C1C(C=1C=CC(C)=CC=1)=CC=C(C=1C=CC(C)=CC=1)C1=CC=C(C)C=C1 LLVWLCAZSOLOTF-UHFFFAOYSA-N 0.000 description 2
- YSTPAHQEHQSRJD-UHFFFAOYSA-N 3-Carvomenthenone Chemical compound CC(C)C1CCC(C)=CC1=O YSTPAHQEHQSRJD-UHFFFAOYSA-N 0.000 description 2
- SEPQTYODOKLVSB-UHFFFAOYSA-N 3-methylbut-2-enal Chemical compound CC(C)=CC=O SEPQTYODOKLVSB-UHFFFAOYSA-N 0.000 description 2
- SSUYASWJXAEBCY-UHFFFAOYSA-N 4-methylpenta-2,4-dien-2-ylphosphonic acid Chemical compound CC(=C)C=C(C)P(O)(O)=O SSUYASWJXAEBCY-UHFFFAOYSA-N 0.000 description 2
- KMRMUZKLFIEVAO-UHFFFAOYSA-N 7,7-dimethylbicyclo[3.1.1]hept-3-ene-4-carbaldehyde Chemical compound C1C2C(C)(C)C1CC=C2C=O KMRMUZKLFIEVAO-UHFFFAOYSA-N 0.000 description 2
- HBAQYPYDRFILMT-UHFFFAOYSA-N 8-[3-(1-cyclopropylpyrazol-4-yl)-1H-pyrazolo[4,3-d]pyrimidin-5-yl]-3-methyl-3,8-diazabicyclo[3.2.1]octan-2-one Chemical class C1(CC1)N1N=CC(=C1)C1=NNC2=C1N=C(N=C2)N1C2C(N(CC1CC2)C)=O HBAQYPYDRFILMT-UHFFFAOYSA-N 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 2
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 239000005973 Carvone Substances 0.000 description 2
- VQTUBCCKSQIDNK-UHFFFAOYSA-N Isobutene Chemical compound CC(C)=C VQTUBCCKSQIDNK-UHFFFAOYSA-N 0.000 description 2
- UIHCLUNTQKBZGK-UHFFFAOYSA-N Methyl isobutyl ketone Natural products CCC(C)C(C)=O UIHCLUNTQKBZGK-UHFFFAOYSA-N 0.000 description 2
- 238000006845 Michael addition reaction Methods 0.000 description 2
- KMRMUZKLFIEVAO-RKDXNWHRSA-N Myrtenal Natural products C1[C@H]2C(C)(C)[C@@H]1CC=C2C=O KMRMUZKLFIEVAO-RKDXNWHRSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- LTTVJAQLCIHAFV-WCBMZHEXSA-N Umbellulone Chemical compound CC1=CC(=O)[C@]2(C(C)C)[C@H]1C2 LTTVJAQLCIHAFV-WCBMZHEXSA-N 0.000 description 2
- LTTVJAQLCIHAFV-UHFFFAOYSA-N Umbellulone Natural products CC1=CC(=O)C2(C(C)C)C1C2 LTTVJAQLCIHAFV-UHFFFAOYSA-N 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000005882 aldol condensation reaction Methods 0.000 description 2
- 125000000746 allylic group Chemical group 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 2
- KMPWYEUPVWOPIM-UHFFFAOYSA-N cinchonidine Natural products C1=CC=C2C(C(C3N4CCC(C(C4)C=C)C3)O)=CC=NC2=C1 KMPWYEUPVWOPIM-UHFFFAOYSA-N 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- HJOVHMDZYOCNQW-UHFFFAOYSA-N isophorone Chemical compound CC1=CC(=O)CC(C)(C)C1 HJOVHMDZYOCNQW-UHFFFAOYSA-N 0.000 description 2
- WUAFXSLROUSYBI-UHFFFAOYSA-N oxaphosphirane Chemical compound C1OP1 WUAFXSLROUSYBI-UHFFFAOYSA-N 0.000 description 2
- 229930006968 piperitone Natural products 0.000 description 2
- 239000002243 precursor Substances 0.000 description 2
- 238000003786 synthesis reaction Methods 0.000 description 2
- 239000004753 textile Substances 0.000 description 2
- DCSCXTJOXBUFGB-UHFFFAOYSA-N verbenone Natural products CC1=CC(=O)C2C(C)(C)C1C2 DCSCXTJOXBUFGB-UHFFFAOYSA-N 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- 229920002554 vinyl polymer Polymers 0.000 description 2
- ZTWTYVWXUKTLCP-UHFFFAOYSA-N vinylphosphonic acid Chemical compound OP(O)(=O)C=C ZTWTYVWXUKTLCP-UHFFFAOYSA-N 0.000 description 2
- REWARORKCPYWIH-UHFFFAOYSA-N 1-(prop-2-enoylamino)butan-2-ylphosphonic acid Chemical compound CCC(P(O)(O)=O)CNC(=O)C=C REWARORKCPYWIH-UHFFFAOYSA-N 0.000 description 1
- GSSDUXHQPXODCN-UHFFFAOYSA-N 1-phenylethenylphosphonic acid Chemical compound OP(O)(=O)C(=C)C1=CC=CC=C1 GSSDUXHQPXODCN-UHFFFAOYSA-N 0.000 description 1
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 1
- GMLDCZYTIPCVMO-UHFFFAOYSA-N 2-methylidenebutanal Chemical compound CCC(=C)C=O GMLDCZYTIPCVMO-UHFFFAOYSA-N 0.000 description 1
- PGKQTZHDCHKDQK-UHFFFAOYSA-N 2-phenylethenylphosphonic acid Chemical class OP(O)(=O)C=CC1=CC=CC=C1 PGKQTZHDCHKDQK-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- 241000219495 Betulaceae Species 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004698 Polyethylene Substances 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ACWQBUSCFPJUPN-UHFFFAOYSA-N Tiglaldehyde Natural products CC=C(C)C=O ACWQBUSCFPJUPN-UHFFFAOYSA-N 0.000 description 1
- ZVQOOHYFBIDMTQ-UHFFFAOYSA-N [methyl(oxido){1-[6-(trifluoromethyl)pyridin-3-yl]ethyl}-lambda(6)-sulfanylidene]cyanamide Chemical compound N#CN=S(C)(=O)C(C)C1=CC=C(C(F)(F)F)N=C1 ZVQOOHYFBIDMTQ-UHFFFAOYSA-N 0.000 description 1
- 239000008186 active pharmaceutical agent Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- FPIPGXGPPPQFEQ-OVSJKPMPSA-N all-trans-retinol Chemical compound OC\C=C(/C)\C=C\C=C(/C)\C=C\C1=C(C)CCCC1(C)C FPIPGXGPPPQFEQ-OVSJKPMPSA-N 0.000 description 1
- 150000001361 allenes Chemical class 0.000 description 1
- 230000000844 anti-bacterial effect Effects 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- 230000000035 biogenic effect Effects 0.000 description 1
- 230000004071 biological effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001805 chlorine compounds Chemical group 0.000 description 1
- 230000002153 concerted effect Effects 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- MLUCVPSAIODCQM-NSCUHMNNSA-N crotonaldehyde Chemical compound C\C=C\C=O MLUCVPSAIODCQM-NSCUHMNNSA-N 0.000 description 1
- MLUCVPSAIODCQM-UHFFFAOYSA-N crotonaldehyde Natural products CC=CC=O MLUCVPSAIODCQM-UHFFFAOYSA-N 0.000 description 1
- 239000012043 crude product Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000006471 dimerization reaction Methods 0.000 description 1
- 239000002270 dispersing agent Substances 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000008030 elimination Effects 0.000 description 1
- 238000003379 elimination reaction Methods 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 229920001002 functional polymer Polymers 0.000 description 1
- 150000004795 grignard reagents Chemical class 0.000 description 1
- 231100001261 hazardous Toxicity 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 238000000589 high-performance liquid chromatography-mass spectrometry Methods 0.000 description 1
- 239000008240 homogeneous mixture Substances 0.000 description 1
- BHEPBYXIRTUNPN-UHFFFAOYSA-N hydridophosphorus(.) (triplet) Chemical compound [PH] BHEPBYXIRTUNPN-UHFFFAOYSA-N 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003317 industrial substance Substances 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- 239000002917 insecticide Substances 0.000 description 1
- 238000004895 liquid chromatography mass spectrometry Methods 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 239000002547 new drug Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical class ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- PJGSXYOJTGTZAV-UHFFFAOYSA-N pinacolone Chemical compound CC(=O)C(C)(C)C PJGSXYOJTGTZAV-UHFFFAOYSA-N 0.000 description 1
- 229920002239 polyacrylonitrile Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000573 polyethylene Polymers 0.000 description 1
- 229920000193 polymethacrylate Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- YOKDQEBPBYOXHX-UHFFFAOYSA-N prop-1-en-2-ylphosphonic acid Chemical compound CC(=C)P(O)(O)=O YOKDQEBPBYOXHX-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 230000009919 sequestration Effects 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 241000894007 species Species 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 150000003573 thiols Chemical group 0.000 description 1
- ACWQBUSCFPJUPN-HWKANZROSA-N trans-2-methyl-2-butenal Chemical compound C\C=C(/C)C=O ACWQBUSCFPJUPN-HWKANZROSA-N 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/38—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)]
- C07F9/3804—Phosphonic acids [RP(=O)(OH)2]; Thiophosphonic acids ; [RP(=X1)(X2H)2(X1, X2 are each independently O, S or Se)] not used, see subgroups
- C07F9/3826—Acyclic unsaturated acids
Definitions
- This invention relates to a method for preparing conjugated diene phosphonate compounds, especially relates to a method for preparing phosphonated monomer with higher reactivity.
- Vinyl monomers containing phosphonic acid groups have various applications in industry, for example, their polymer and co-polymers are used as corrosion inhibitor in cooling or boiler water system (US 4,446,046 and 4,201,669); as dispersants in water treatment and pigment dispersion.
- vinyl monomers such as 1-phenylvinyl phosphonic acid (US 5391,816), vinyl phosphonic acid (US 6,479,687, 5,811,575), acrylamidomethylpropanephosphonic acid (US 4,526,788), isopropenyl phosphonic acid (US4,446,046), chloride substituted phenylvinyl phosphonic acid (US 4,507,249) and diene type of phosphonic acid monomer (US 4,507,249).
- 1-phenylvinyl phosphonic acid US 5391,816)
- vinyl phosphonic acid US 6,479,687, 5,811,575
- acrylamidomethylpropanephosphonic acid US 4,526,788
- isopropenyl phosphonic acid US4,446,046)
- chloride substituted phenylvinyl phosphonic acid US 4,507,249
- diene type of phosphonic acid monomer US 4,507,249
- Recent US 7,420,081 and 7,442,831 patents described a new way to prepare some of the above monomers from ketone or aldehyde with phosphorous acid in a mixture of acetic acid and acetic anhydride. These monomers include alkyl and aryl substituted vinyl phosphonic acids of lower reactivity toward polymerization. It is still desirable to have an economic process to produce more reactive phosphonic acid-containing monomers.
- this invention relates to a method for preparing conjugated diene phosphonate compounds with high reactivity, which comprises the step of reacting ⁇ , ⁇ - or ⁇ , ⁇ -unsaturated ketones or aldehydes having the formula I or II, with phosphorous acid or its derivatives optionally in a mixture of acetic anhydride and/or acetic ac
- the method of the present invention can be used to prepare a variety of phosphonate-bearing conjugated dienes. Some of those dienes will become reactive monomers to make performance polymers and co-polymers. These polymers could find applications in water treatment, oilfield applications, surface treatment applications, mining, dental application, plastics, etc.
- the monomers prepared according to the present invention alone could be used for the previous applications and provide the advantage that they could be polymerized at surfaces much easier than current commercial monomers.
- the present invention provides a method for preparing conjugated diene phosphonate compounds from ⁇ , ⁇ - or ⁇ , ⁇ -unsaturated ketones or aldehydes, which comprises reacting an ⁇ , ⁇ - or ⁇ , ⁇ -unsaturated ketone or aldehyde having the formula I or
- Ri, R 2 , R 3 , R4, and R5 represent, independently, hydrogen, alkyl, aryl, alkaryl, aralkyl, cycloalkyl, heterocycloalkyl, or alkenyl groups; preferably, the said alkyl and alkenyl comprise from 1-24 carbon atoms, said aryl comprises from 6-24 carbon atoms, said alkaryl, aralkyl comprise from 7-24 carbon atoms, and said cycloalkyl, heterocycloalkyl comprise from 3-24 carbon atoms; more preferably, the said alkyl and alkenyl comprise from 1-18 carbon atoms, said aryl comprises from 6-18 carbon atoms, said alkaryl, aralkyl comprise from 7-18 carbon atoms, and said cycloalkyl, heterocycloalkyl comprise from 3-18 carbon atoms.
- Ri and/or R 2 represent hydrogen, so the monomers so obtained are more reactive toward polymerization.
- Ri, R 2 and R4 represent hydrogen; or preferably, R 3 and R5 represent methyl. More preferably, Ri, R 2 , and R4 represent hydrogen and R 3 , R5 represent methyl.
- R6 and R 7 represent, independently, hydrogen, alkyl, aryl, alkaryl, aralkyl, cycloalkyl, alkenyl groups, or metals selected from the group consisting of Na, Li, Ca.
- the said alkyl and alkenyl comprise from 1-24 carbon atoms
- said aryl comprises from 6-24 carbon atoms
- said alkaryl, aralkyl comprise from 7-24 carbon atoms
- said cycloalkyl, heterocycloalkyl comprise from 3-24 carbon atoms
- the said alkyl, alkenyl comprise from 1-18 carbon atoms
- said aryl comprises from 6-18 carbon atoms
- said alkaryl, aralkyl comprise from 7-18 carbon atoms
- said cycloalkyl, heterocycloalkyl comprise from 3-18 carbon atoms.
- R6, and R 7 represent hydrogen.
- any two of Ri, R 2 , R 3 , R4 and R5 are together formed into a cycloalkyl, or heterocycloalkyl group, which is preferably selected from 5, 6, 7 and 8 membered rings.
- R 6 and R 7 are together formed into a cycloalkyl, or heterocycloalkyl group, which is preferably selected from 5, 6, 7 and 8 membered rings.
- the compounds of the present invention may contain one or more chiral centers and/or double bonds and therefore may exist as stereoisomers, such as Z- and E- or cis- and trans-isomers from cyclic structures or double bonds (i.e., geometric isomers), rotamers, enantiomers or diastereomers. Accordingly, when stereochemistry at chiral centers is not specified, the chemical structures depicted herein encompass all possible configurations at those chiral centers including the stereoisomerically pure form (e.g.
- said compound I or II is added in the molar ratio of (1-1.5) ' . 1 relative to said phosphorous acid or its derivatives; or preferably (1-1.2) ' . 1 relative to said phosphorous acid or its derivatives.
- the reaction time remains 4-24 hours, or preferably 4-8 hours.
- the reaction temperature remains at 0-100 ° C , or preferably 20-60 ° C .
- the reaction according to the present invention may be optionally carried out under protection of inert gas protection.
- Said inert gas may be selected from, for example, one or more of the group consisting of nitrogen, argon, and carbon dioxide.
- the preparation method of the present invention is valid whether starting from ⁇ , ⁇ -unsaturated carbonyl compounds or ⁇ , ⁇ -unsaturated carbonyl compounds and both species will lead to the formation of the same diene.
- mesityl oxide was reacted with phosphorous acid in the presence of acetic anhydride and acetic acid under mild conditions to yield 4-methylpenta-2,4-diene-2-phosphonic acid in more than 90% mole purity.
- the unsaturated ketones and aldehydes can be obtained from aldol condensations of carbonyl compounds.
- MIBK methyl isobutyl ketone
- ketones and aldehydes are important industrial chemicals. They are used as solvents, for example, mesityl oxide, as precursor to other commodity and specialty chemicals, for example, isophorone and as monomer for polymeric materials, for example, methyl vinyl ketone (MVK).
- solvents for example, mesityl oxide
- isophorone as precursor to other commodity and specialty chemicals, for example, isophorone and as monomer for polymeric materials, for example, methyl vinyl ketone (MVK).
- MVK methyl vinyl ketone
- 3-Methylcrotonaldehyde is a precursor for Vitamine A. Industrially, it is produced from isobutene and formaldehyde:
- the most attractive one may be crotonaldehyde. It is a biogenic compound, used as florvoring agent. It can be produced from renewable resources of bioethanol:
- Natural unsaturated ketones and aldehydes can also be used to carry out the reaction. Those include, for example, piperitone, carvone, umbellulone, menthene-2-one, menthene-3-one, verbenone and myrtenal.
- the resulting phosphonate dienes could be of important biological activities, thus as insecticides, pesticides, pharmaceuticals and their intermediates.
- the phosphonate diene prepared according to the method of the present invention can be used for making polymers or co-polymers, hi this aspect the invention also relates to a polymer or co-polymer of said conjugated diene phosphonate compounds.
- the invention also relates to a method for preparing polymers or co-polymers of the phosphonate diene, comprising a step of preparing a phosphonate diene according to the method of the present invention and a polymerization or co-polymerization step.
- the phosphonate diene prepared according to the method of the present invention, or the polymer or co-polymer can be used as flame retardants, as intermediates for active pharmaceuticals and agrochemicals, as reactive or functional monomers, typically for functional polymers, such as phosphonate-containing polystyrene, polyethylene, polypropylene, poly(meth)acrylates, poly(meth)acrylamide, polybutadiene, polyacrylonitrile, etc. and their copolymers, or building blocks for other useful products.
- functional polymers such as phosphonate-containing polystyrene, polyethylene, polypropylene, poly(meth)acrylates, poly(meth)acrylamide, polybutadiene, polyacrylonitrile, etc. and their copolymers, or building blocks for other useful products.
- the phosphonate diene prepared according to the method of the present invention, or the polymer or co-polymer can be used in water treatment applications, in oilfield applications, in surface treatment applications, in mining applications, in dental applications, in plastics, and etc...
- the phosphonate diene prepared according to the method of the present invention, or the polymer or co-polymer can be used as flame retardants in plastics or textile.
- the invention also relates to methods comprising these uses.
- Phosphonate functionalities are well known to provide flame retardant (FR) properties but their synthesis is often difficult and expensive.
- the process according to the present invention allows a direct access to phosphonate moieties from inexpensive raw materials.
- the products obtained can also be further reacted to prepare some polymers.
- the monomers and/or the polymers should provide some significant flame retardant properties if incorporated to plastics, textiles or any other materials.
- the conjugated dienes prepared according to the process of the present invention may be active or intermediates for pharmaceuticals or/and agroculture chemicals.
- Phosphonate compounds are well known to have unique properties and are widely used in the pharmaceutical industry. The compounds described here would provide new and unique entitis that could be used to design new drugs. These compounds could also find some use in agriculture.
- Phosphonate monomers are scarce and typically difficult and expensive to prepare. Also, most of them have a limited reactivity which makes them difficult to use as functional monomers to combine them with other monomers (styrene, ethylene, butadiene, acrylic acid etc .). Incorporating phosphonate moieties into polymers can provide unique properties to the resulting materials such as better mechanical properties, flame reardant properties, sequestration properties, anti-bacterial properties etc. the diene monomer can also be grafted onto synthetic or natural occurring polymers.
- the present invention also provides polymers prepared from conjugated diene phosphonate compounds of the formula III according to the present invention.
- R 7 can be H.
- the invention provides a process to make 1,3-diene phosphonate in one step under mild conditions and using readily available and affordable raw materials. This process is a significant improvement in term of ease of process and cost.
- the 1,3-diene phosphonate prepared according the present invention allows to develop some original polymers and composition that were not accessible before.
- the technical solution of the present invention is kind to the environment. Using sustainable and natural raw materials is critical today and many unsaturated ketones or aldehydes are actually natural products.
- H 3 PO 3 was dried for about 4 hrs at 50 ° C under vacuum. lOg of dried H 3 PO 3 and 12.43 g of mesityl oxide were mixed in a flask at 28-30 ° C . Then 24.7 g of acetic anhydride was added slowly with mixing over 50 mins while the reaction temperature was kept below 30 ° C . The mixture was kept stirring at this temp for 4 hrs. 31 P NMR showed 81.2% conversion of H 3 PO 3 and 86% selectivity for PoDM and its anhydride derivatives.
- H 3 PO 3 was dried for about 4 hrs at 50 ° C under vacuum. lOg of dried H 3 PO 3 was dissolved in 9.7 g of acetic acid to make solution A. Then 14.2 g of mesityl oxide, 24.7 g of acetic anhydride and 0.0 lg of Phenothiazine was charged in a flask and heated to 60 ° C . Solution A was added dropwise. The mixture was kept stirring at 60 ° ° C for 4 hrs. 31 P NMR showed 88.3% conversion of H 3 PO 3 and 86% selectivity for PoDM and its anhydride derivatives.
- H 3 PO 3 was dried for about 4 hrs at 50 ° C under vacuum. lOg of dried H 3 PO 3 was dissolved in 12.35 g of acetic acid to make solution A. Then 14.2 g of mesityl oxide, 12.35 g of acetic anhydride and 0.01 g of phenothiazine was mixed together to make solution B. Next a three-necked flask was put in a oil bath at 60 ° C and then Solutions A and B were added dropwise and simultaneously over 70 min. After the addition, the mixture was kept stirring for another 4 hrs. 31 P NMR showed 97.5% conversion of H 3 P0 3 and 87% selectivity for PoDM and its anhydride derivatives.
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PCT/CN2009/074726 WO2011050533A1 (en) | 2009-10-30 | 2009-10-30 | Method for preparing conjugated diene phosphonate compounds |
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EP (1) | EP2493903A4 (de) |
JP (1) | JP5559341B2 (de) |
KR (1) | KR20120127398A (de) |
CN (1) | CN102596975A (de) |
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FR2997405B1 (fr) * | 2012-10-29 | 2015-11-13 | Rhodia Operations | Utilisation d'une silice precipitee contenant du titane et d'un agent de couplage specifique dans une composition d'elastomere(s) |
CN110903318B (zh) * | 2019-12-23 | 2023-02-28 | 西北民族大学 | 一种烯基膦酸酯化合物的制备方法 |
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US4507249A (en) * | 1982-03-22 | 1985-03-26 | Hoechst Aktiengesellschaft | Process for making derivatives of vinylphosphonic acid or vinylpyrophosphonic acid |
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US2389576A (en) * | 1943-08-16 | 1945-11-20 | Monsanto Chemicals | Esters of diolefinic phosphonic acids |
US2486657A (en) * | 1945-04-28 | 1949-11-01 | Monsanto Chemicals | Diolefin phosphonic acids and polymers thereof |
US4170609A (en) | 1973-08-20 | 1979-10-09 | Turner William F | Aldol condensation process |
US4201669A (en) | 1978-09-11 | 1980-05-06 | Betz Laboratories, Inc. | Deposit control through the use of oligomeric phosphonic acid derivatives |
DE3033615A1 (de) * | 1980-09-06 | 1982-09-30 | Hoechst Ag, 6000 Frankfurt | Verfahren zur herstellung von vinylphosphonsaeurederivaten und deren verwendung |
JPS57104894A (en) * | 1980-12-23 | 1982-06-30 | Tokyo Shibaura Electric Co | Test device for reactor circulation system |
US4446046A (en) | 1981-06-17 | 1984-05-01 | Betz Laboratories, Inc. | Poly (alkenyl) phosphonic acid and methods of use thereof |
CA1183861A (en) * | 1981-06-17 | 1985-03-12 | Larry W. Becker | Poly(alkenyl) phosphonic acid and methods of use thereof |
US4526788A (en) | 1983-03-18 | 1985-07-02 | American Cyanamid Company | Polymeric[[(oxazolidinyl)alkyl]amino]anthraquinones |
JPS6133137A (ja) | 1984-07-24 | 1986-02-17 | Sumitomo Chem Co Ltd | チグリルアルデヒドの製造方法 |
US5391816A (en) | 1993-11-08 | 1995-02-21 | Akzo Nobel N.V. | Formation of 1-phenylvinyl-1-phosphonic acid |
DE4416018A1 (de) | 1994-05-06 | 1995-11-09 | Hoechst Ag | Verfahren zur Herstellung von Vinylphophonsäuren |
US5783730A (en) * | 1997-05-02 | 1998-07-21 | Akzo Nobel Nv | Formation of styrene phosphonic acid |
WO2000078387A1 (en) | 1999-06-22 | 2000-12-28 | Blanco Ernesto E | Safety trocar with progressive cutting tip guards and gas jet tissue deflector |
EP1169996A1 (de) * | 2000-07-06 | 2002-01-09 | Ernst Mühlbauer Kg | Phosphonsäuren enthaltendes Dentalmaterial |
JP4207115B2 (ja) * | 2002-12-26 | 2009-01-14 | 日産化学工業株式会社 | リン系有機基含有高分子を含む反射防止膜形成組成物 |
US7442831B2 (en) * | 2004-07-07 | 2008-10-28 | Unichem Technologies, Inc. | Methods of synthesizing phosphonic compounds and compounds thereof |
CN101343289A (zh) * | 2008-08-25 | 2009-01-14 | 苏州大学 | 一种合成有机膦酸酯衍生物的方法 |
WO2011050537A1 (en) * | 2009-10-30 | 2011-05-05 | Rhodia (China) Co., Ltd. | Conjugated diene phosphinate compounds, preparation method and use thereof |
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- 2009-10-30 EP EP09850739A patent/EP2493903A4/de not_active Withdrawn
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KR20120127398A (ko) | 2012-11-21 |
JP5559341B2 (ja) | 2014-07-23 |
CN102596975A (zh) | 2012-07-18 |
BR112012009354A2 (pt) | 2016-11-22 |
US20120202957A1 (en) | 2012-08-09 |
JP2013509354A (ja) | 2013-03-14 |
US8895775B2 (en) | 2014-11-25 |
WO2011050533A1 (en) | 2011-05-05 |
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